Bis-epoxycyclopentanyl ether



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2,739,161 BIS-EPOXYCYCLOPENTANYL ETHER Arthur w. Carlson, Chicago, Ill., assignor to Velsicol Chemical Corporation, a corporation of Illinois Application December 16, 1954, Serial No. 475,841

1 Claim. (Cl. 260-348) No Drawing.

This invention relates to new epoxide-ether compositions of matter. More specifically, this invention relates to the diepoxide of bis-cyclopentenyl ether andto resin compositions derived therefrom. The diepoxide of biscyclopentenyl ether may be illustrated by the structure The composition of the present invention is a color- 9 late evaporation and provide the linger associated with better perfumes. Since in many cases these ingredients are unsaturated materials, they have a tendency to become rancid when exposed to body heat and air. To counteract this property, it has been necessary to add certain stabilizers to the perfume formulation. The present composition is especially useful in this respect as it provides a stabilizing action and concomitantly contributes to the fragrance of the formulation. This property is seen most advantageously when incorporatd into proprietary toiletry goods such as soaps, creams, skin lotions, hair dressings and cosmetics of a broad variety which contain such unsaturated materials.

These compounds are further useful as stabilizers for resins in general and are particularly valuable as stabilizers for resins containing chlorine such as polyvinyl chloride, neoprene, vinylidene chloride, chlorendic acid polyesters, and the like, and also for chlorine containing insecticides such as endrin, dieldrin and the like.

Aside from stabilizer properties which are inherent in the products of the present invention, they are reactive organic epoxides which upon treatment with certain ionic catalysts form polyether resins. These polyether resins can be formed from bis-cyclopentenyl ether diepoxide alone or can be prepared'with other epoxy materials to form a copolymeric polyether resin which has the desirable properties imparted by the products of the present invention. Epoxides which are useful in compounding these copolymeric polyethers are styrene oxides, propylene oxide, butylene oxide, vinyl cyclo hexene oxide, allyl glycidyl ether, dicyclopentadiene epoxide and the like. -r

The acidic catalysts suitable for catalyzing this reaction are BFa, AlCls, SnClr, ZnClz, HISPOI, and the like.

The starting material for the present composition, biscyclopentenyl ether, is prepared initially from cyclopentadiene. The mode of preparation is disclosed in my copending United States patent application, Serial No. 352,040, filed April 29, 1953. The process substantially Zfldddl Patented Mar. 20, 1956 involves addition of HCl to cyclopentadiene to produce 3-chlorocyclopentene which is hydrolyzed with weak aqueous alkali to produce the corresponding hydroxy compound. The alcohol readily forms the ether by acid catalysis in high yield and is recovered by vacuum distillation.

The epoxidation of bis-cyclopentenyl ether is accomplished by the use of an organic per acid reagent such as peracetic acid, perbenzoic acid, or monoperphthalic acid. Generally, a slight molar excess of the peracid re agent is desirable and about a molar excess is preferred. The temperature of peroxidation should be below about C. and preferably from about 10 C. to about 25 C. Pressure is not a critical factor in the present invention and atmospheric pressures can be used or pressures either slightly above or below atmospheric pressure are suitable. 1

The following examples will illustrate the method of preparing the starting material and final product.

EXAMPLE I A. Preparation of 3-chl0r0cyclopentene Into a /2 liter, 3-necked flask equipped with a stirrer, gas inlet sparger and reflux condenser, was placed cyclopentadiene (132 grams; 2 moles). While maintaining the cyclopentadiene at a temperature of about -20 C., gaseous HCl was continuously introduced into the flask below the liquid surface at a rate sufiicient to maintain a saturated solution of HCl in cyclopentadiene. The reaction is exothermic and the temperature was maintained below about -15 C. The'addition of I-ICl was discontinued after about two hours and the desired 3-chlor0- cyclopentene was recovered by fractional distillation in vacuo. The 3-chlorocyclopentene boiled at 25 C. and 30 mm. Hg pressure. The yield of product was about based on cyclopentadiene utilized.

B. Preparation of 3-hydroxycyclopenteng A. solution of potassium carbonate (.694 grams; 5 moles) in water (1000 ml.) was introduced into a dropping funnel. 3-chlorocyclopentene. (513 grams; 5 moles) was likewise introduced into a different dropping funnel and maintained at a temperature of about 50-" C. The contents of the two separatory funnels were simultane! ously and continuously introduced at a constant rate into a reaction vessel containing water maintained at 5 to 10 C. The rate of introduction of the two reactants was such as to require about 1.5 hours to empty the two dropping funnels. During addition of the reactants to the reaction vessel, the reaction mixture was constantly and vigorously stirred and maintained at a temperature of about 5 to 10 C. When the reactants had been completely added to the reaction vessel, stirring of the mixture was continued and the temperature was slowly increased to normal room temperature. The reaction mixture was then filtered to remove undissolved material and the organic layer of the filtrate was separated from the aqueous layer. The aqueous fraction was extracted several times with small portions of diethyl ether and the extracts were combined with the organic fraction. This combined organic material was then washed several times with a saturated solution of sodium chloride in water and was then dried successively over anhydrous sodium sulfate and potassium carbonate. The ether solvent was removed by distillation in vacuo and the residue was further fractionated by distillation in vacuo lyst. Bis-(Z-cyclopentenyl) ether can also be prepared from 3-chlorocyclopentene in one step without isolating the intermediate hydroxy compound as is shown in part C immediately hereafter. V

C. Preparation of bis-(Z-cyclopentenyl) ether The process stated in part B was duplicated in every detail to the point where the reactants had been completely added to the reaction vessel. The reaction mixture was then stirred for an additional two hours without external cooling. The reaction mixture was then neutralized with concentrated hydrochloric acid and ml. excess concentrated hydrochloric acid was. then added thereto. Stirring was continued for about 2.5 hours at room temperature and then the mixture was permitted to stand about 16 hours. The organic layer of the reaction mixture was removed from the aqueous layer and 'washed thoroughly with water. The washed organic fraction was dried over anhydroux potassium carbonate and then fractionally distilled in vacuo. pentenyl) ether was recovered as a colorless liquid boiling at 64-65 C. under 9 mm. Hg pressure. The following analysis was obtained for this desired intermediate:

EXAMPLE II Preparation of bis-cyclopentenyl ether diepoxide Dicyclopentenyl ether (2.0 mol. 300.4. g.) was placed in a three-necked flask equipped with a stirrer, reflux condenser, thermometer, and separatory funnel. Peracetic acid 40% (4. r mol. 836 g.) previously treated with sodium acetate (14 g.) was introduced dropwise for 2.5 hours. The temperature during the above addition and throughout the entire reaction was maintained at l5-20 C. After addition was complete the reaction mixture was stirred for an additional five hours, and the contents of the flask were then neutralized with KOH. The contents of the flask were extracted with ether several times and the combined extracts dried over anhydrous KzCOa. The ether solvent was removed by evaporation and the liquid residue was subjected to careful vacuum fractional distillation. The diepoxide was recovered as the fraction boiling 122153 C./5 mm. Hg pressure.

The forerun contained 5% diepoxide and 3% monoepoxide which may be recovered by a recycling process. The foregoing examples illustrate a method of prepar- Bis- Z-cyclo- 4 ing bis-cyclopentenyl ether diepoxide. Polymers may be prepared from this material as aforementioned using BFa catalyst. The following example will illustrate the method of preparation.

I EXAMPLE III Into a S-necked flask equipped with a stirrer, reflux condenser and addition tunnel was placed 6 grams (0.03 mole) of bis-cyclopentenyl ether diepoxide and 25 ml. of a solution of 0.1 g. of BFa and 1 ml. of butanol in 50 mi. of toluene chilled to 0 C. The mixing of the contents of the reaction vessel caused the temperature to rise in the exothermic reaction to 20 C. where it was maintained for four hours of stirring. At the end of this time fullers earth was added to neutralize the BR, and the resin solution recovered as filtrate. Toluene solvent was removed by vacuum distillation and the resinous product dried under vacuum. The product was a solid resin which softened at about 300 C. but did not melt. The resin wasinsoluble in mineral spirits, acetone, isopropyl ether, and isobutyl methyl ketone. The resin was soluble in toluene, chloroform, methyl Cellosolve and butyl Carbitol.

If desired, the product of the present invention can be polymerized with other catalysts similar to BFa, such as AlCls ZnClz, HF, hydrofluoric acid treated clay and the like.

- The present composition can also be used to prepare copolyme'ric materials using other epoxides. For example, a copolymer having unusual physical properties has been prepared by using equimolar quantities of bis-cyclopentenyl ether diepoxide and propylene oxide as reactants and BE; in toluene as catalyst. Other epoxides such as ethylene oxide, styrene oxide, propylene oxide, vinyl cyclohexene oxide, butylene oxide, and the like can also be utilized to prepare a variety of useful copolymers which have the moiety of the present composition as a common characteristic reacted therein.

I claim: As a new composition of matter a compound of the structure HOH References Cited in the tile of this patent UNITED STATES PATENTS Niederhauser Feb. 27, 1951 

